Antibacterial and antifungal composition

ABSTRACT

An antibacterial and antifungal composition comprising (A) at least one member selected from the group consisting of dehydroacetic acid, sorbic acid and their alkali metal salts and (B) at least one member selected from the group consisting of o-phenylphenol and its alkali metal salts, p-chloro-m-xylenol, 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline and its salts and chelates, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile and N-(fluorodichloromethylthio)phthalimide. The antibacterial and antifungal effects can be synergistically increased when the component (A) is employed in combination with the component (B).

This is a continuation of application Ser. No. 058,448, filed July 18, 1979, now U.S. Pat. No. 4,242,386, issued Dec. 30, 1980.

BACKGROUND OF THE INVENTION

The present invention relates to a composition useful as antibacterial and antifungal agent, and more particularly to a composition mainly containing dehydroacetic acid, sorbic acid or their alkali metal salts.

It is well known that dehydroacetic acid, sorbic acid and their alkali metal salts are useful as antibacterial and antifungal agents. The toxicity of these antibacterial and antifungal agents is so low that their addition to foods is permitted, and they are agents of very high safety. Therefore, if these agents are usable in any fields such as general industrial products and agricultural products, to say nothing of foods, the usefulness of these agents becomes very great. However, the antibacterial and antifungal effects thereof are not always satisfactory, and they are restricted in the application to industrial products such as paints, sizing agents and adhesives.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided an antibacterial and antifungal composition comprising (A) at least one member selected from the group consisting of dehydroacetic acid, sorbic acid and their alkali metal salts and (B) at least one member selected from the group consisting of o-phenylphenol and its alkali metal salts, p-chloro-m-xylenol, 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline and its salts and chelates, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile and N-(fluorodichloromethylthio)phthalimide. The synergistic effect on the antibacterial and antifungal properties is very remarkable, when the component (A) is employed in combination with the component (B), and the composition of the invention can be availably employed as antibacterial and antifungal agents in various industrial products and agricultural products.

DETAILED DESCRIPTION

There are employed, as the component (A) of the composition of the invention, dehydroacetic acid, sorbic acid and their alkali metal salts such as sodium dehydroacetate, potassium dehydroacetate, sodium sorbate and potassium sorbate. These compounds may be employed alone or in admixture thereof.

Examples of a compound employed as the component (B) of the composition of the invention are o-phenylphenol and its alkali metal salts shown by the following formula: ##STR1## wherein X is hydrogen or an alkali metal, p-chloro-m-xylenol shown by the following formula: ##STR2## 2-(4-thiazolyl)-1H-benzimidazole shown by the following formula: ##STR3## 8-hydroxyquinoline shown by the following formula: ##STR4## salts of 8-hydroxyquinoline with organic or inorganic acids such as hydrochloric acid, sulfuric acid and acetic acid, e.g. 8-hydroxyquinoline sulfate of the formula: ##STR5## chelates of 8-hydroxyquinoline with metals such as copper and zinc, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate shown by the following formula: ##STR6## tetrachloroisophthalonitrile shown by the following formula: ##STR7## and N-(fluorodichloromethylthio)phthalimide shown by the following formula: ##STR8## These compounds may be employed anone or in admixture thereof.

The components (A) and (B) may be employed in any proportions. In general, it is desirable to employ the component (B) in an amount of 1% to 40% by weight based on the total weight of the composition, since the particularly remarkable synergistic effect can be obtained. As stated before, the feature of the present invention is that the antibacterial and antifungal effects of dehydroacetic acid, sorbic acid or their alkali metal salts can be remarkably increased by the combination use with a slight amount of the component (B). Although the compounds employed as the component (B) are known as antibacterial and antifungal agents, it has now been found that synergistic antibacterial and antifungal effect unexpected from a single use of various known antibacterial and antifungal agents can be obtained, when among known antibacterial and antifungal agents the component (A) and the component (B) are particularly combined. When the content of the component (B) is less than 1% by weight, sufficient synergistic effect cannot be obtained. Also, even if the component (B) is employed in an amount of more than 40% by weight, the synergistic effect is not increased. Further, the compounds employed as the component (B) are relatively expensive and also the toxicity is higher than the component (A) and, therefore, the use of the component (B) in an amount of more than 40% by weight not only be uneconomical, but also may impair the low toxicity which is the feature of the composition of the present invention.

The adding amount of the composition varies depending on the kind of the products to be added. In general, sufficient antibacterial and antifungal effects can be obtained in an amount of 50 to 8,000 p.p.m.

Auxiliary agents such as other bactericides, other fungicides, surface active agents and perfumes may be incorporated in the composition of the invention, as occasion demands.

The composition of the present invention is applicable to any industrial products and agricultural products which require the annihilation or the prevention of propagation of bacteria and fungi, such as paints, sizing agents, petroleum products, plastic moldings, fibers, leathers, woods, paper goods, cosmetics, pharmaceuticals, medical appliances, industrial equipments and building materials (putties, fiber boards, particle boards, gypsum boards), fruits, grains and vegetables.

The present invention is more particularly described and explained by means of the following Examples, in which all % are by weight unless otherwise noted.

EXAMPLE 1

A liquid culture medium of pH 7.0 containing 1% of peptone, 1% of meat extract and 0.1% of sodium chloride was prepared and sterilized, and 10 ml. portions thereof were poured into L-shaped tubes. After adding a prescribed amount of an antibacterial, antifungal composition consisting of the components (A) and (B) as shown in Table 1 to each tube, 0.1 ml. (number of cells: 5×10⁴ cells/ml.) of an aqueous suspension of bacteria as shown in Table 1 was added to each tube. The thus prepared culture liquor contained 5×10² cells per milliliter. The culture was carried out at 37° C. for 48 hours with reciprocal shaking, and the state of the growth of bacteria was then observed by measuring the number of cells in 1 ml. of the culture liquor.

The results are shown in Table 1.

                                      TABLE 1                                      __________________________________________________________________________                                           Amount of                                       Antibacterial, antifungal composition                                                                         composition                                                                          Number of                                                          (A)/(B)                                                                              added cells                              Bacteria                                                                              Component (A)                                                                              Component (B)                                                                               by weight                                                                            (p.p.m.)                                                                             (cells/ml.)                        __________________________________________________________________________     Staphylococ-                                                                          Sodium dehydroacetate                                                                      N-(fluorodichloro-                                                                          95/5  500   25 × 10                      cus aureus         methylthio)phthalimide                                                                      95/5  1000  3 × 10                                                       90/10 500   18 × 10                                                      90/10 1000  0                                                                  80/20 500   17 × 10                                                      80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   19 × 10.sup.5                                                100/0 1000  18 × 10.sup.3                                                0/100 25    11 × 10.sup.8                                                0/100 50    10 × 10.sup.5                                                0/100 100   7 × 10.sup.4                                                 0/100 200   6 × 10.sup.2                 Staphylococ-                                                                          Potassium sorbate                                                                          N-(fluorodichloro-                                                                          95/5  500   30 × 10                      cus aureus         methylthio)phthalimide                                                                      95/5  1000  6                                                                  90/10 500   22 × 10                                                      90/10 1000  0                                  Staphylococ-                                                                          Potassium sorbate                                                                          N-(fluorodichloro-                                                                          80/20 500   14 × 10                      cus aureus         methylthio)phthalimide                                                                      80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   25 × 10.sup.7                                                100/0 1000  9 × 10.sup.5                                                 0/100 25    11 × 10.sup.8                                                0/100 50    10 × 10.sup.5                                                0/100 100   7 × 10.sup.4                                                 0/100 200   6 × 10.sup.2                 Staphylococ-                                                                          Sorbic acid N-(fluorodichloro-                                                                          95/5  500   25 × 10                      cus aureus         methylthio)phthalimide                                                                      95/5  1000  0                                                                  90/10 500   15 × 10                                                      90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   21 × 10.sup.6                                                100/0 1000  5 × 10.sup.3                                                 0/100 25    11 × 10.sup.8                Staphylococ-                                                                          Sorbic acid N-(fluorodichloro-                                                                          0/100 50    10 × 10.sup.5                cus aureus         methylthio)phthalimide                                                                      0/100 100   7 × 10.sup.4                                                 0/100 200   6 × 10.sup.2                 Bacillus                                                                              Sodium dehydroacetate                                                                      Sodium o-phenylphenolate                                                                    95/5  500   9 × 10                       subtilis                        95/5  1000  7                                                                  90/10 500   8 × 10                                                       90/10 1000  0                                                                  80/20 500   6 × 10                                                       80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   23 × 10.sup.7                                                100/0 1000  9 × 10.sup.4                                                 0/100 25    3 × 10.sup.7                                                 0/100 50    15 × 10.sup.4                                                0/100 100   6 × 10.sup.3                                                 0/100 200   9 × 10                       Bacillus                                                                              Potassium sorbate                                                                          Sodium o-phenylphenolate                                                                    95/5  500   15 × 10                      subtilis                        95/5  1000  2                                                                  90/10 500   12 × 10                                                      90/10 1000  1                                                                  80/20 500   6 × 10                                                       80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   7 × 10.sup.8                                                 100/0 1000  5 × 10.sup.7                                                 0/100 25    3 × 10.sup.7                                                 0/100 50    15 × 10.sup.4                                                0/100 100   6 × 10.sup.3                                                 0/100 200   9 × 10                       Bacillus                                                                              Sorbic acid Sodium o-phenylphenolate                                                                    95/5  500   15 × 10                      subtilis                        95/5  1000  0                                                                  90/10 500   7 × 10                                                       90/10 1000  0                                                                  80/20 500   3 × 10                       Bacillus                                                                              Sorbic acid Sodium o-phenylphenolate                                                                    80/20 1000  0                                  subtilis                        60/40 500   0                                                                  100/0 500   13 × 10.sup.6                                                100/0 1000  18 × 10.sup.4                                                0/100 25    3 ×10.sup.7                                                  0/100 50    15 × 10.sup.4                                                0/100 100   6 × 10.sup.3                                                 0/100 200   9 × 10                       Staphylococ-                                                                          Sodium dehydroacetate                                                                      2-(4-Thiazolyl)-1H-                                                                         95/5  500   21 × 10                      cus aureus         benzimidazole                                                                               95/5  1000  6 × 10                                                       90/10 500   20 × 10                                                      90/10 1000  9                                                                  80/20 500   19 × 10                                                      80/20 1000  8                                                                  60/40 500   8 × 10                                                       60/40 1000  5                                                                  100/0 500   19 ×  10.sup.5                                               100/0 1000  18 × 10.sup.3                Staphylococ-                                                                          Sodium dehydroacetate                                                                      2-(4-Thiazolyl)-1H-                                                                         0/100 25    4 × 10.sup.9                 cus aureus         benzimidazole                                                                               0/100 50    4 × 10.sup.8                                                 0/100 100   10 × 10.sup.6                                                0/100 200   5 × 10.sup.4                 Staphylococ-                                                                          Potassium sorbate                                                                          2-(4-Thiazolyl)-1H-                                                                         95/5  500   25 × 10                      cus aureus         benzimidazole                                                                               95/5  1000  8 × 10                                                       90/10 500   24 × 10                                                      90/10 1000  15                                                                 80/20 500   31 × 10                                                      80/20 1000  15                                                                 60/40 500   29 × 10                                                      60/40 1000  10                                                                 100/0 500   25 × 10.sup.7                                                100/0 1000  9 × 10.sup.5                                                 0/100 25    4 × 10.sup.9                                                 0/100 50    4 × 10.sup.8                                                 0/100 100   10 × 10.sup.6                                                0/100 200   5 × 10.sup.4                 Staphylococ-                                                                          Sorbic acid 2-(4-Thiazolyl)-1H                                                                          95/5  500   30 × 10.sup.2                cus aureus         benzimidazole                                                                               95/5  1000  15 ×  10                                                     90/10 500   41 × 10                                                      90/10 1000  35                                                                 80/20 500   17 × 10                                                      80/20 1000  10                                                                 60/40 500   6 × 10                                                       60/40 1000  5                                                                  100/0 500   21 × 10.sup.6                                                100/0 1000  5 × 10.sup.3                                                 0/100 25    4 × 10.sup.9                                                 0/100 50    4 × 10.sup.8                                                 0/100 100   10 × 10.sup.6                                                0/100 200   5 × 10.sup.4                 Staphylococ-                                                                          Sodium dehydroacetate                                                                      Methyl 1-(butylcarba-                                                                       95/5  500   23 × 10                      cus aureus         moyl)-2-benzimidazole-                                                                      95/5  1000  5                                                     carbamate    90/10 500   21 × 10                                                      90/10 1000  0                                  Staphylococ-                                                                          Sodium dehydroacetate                                                                      Methyl 1-(butylcarba-                                                                       80/20 500   20 × 10                      cis aureus         moyl)-2-benzimidazole-                                                                      80/20 1000  0                                                     carbamate    60/40 500   0                                                                  100/0 500   19 × 10.sup.5                                                100/0 1000  18 × 10.sup.3                                                0/100 25    7 × 10.sup.6                                                 0/100 50    9 × 10.sup.4                                                 0/100 100   12 × 10.sup.2                                                0/100 200   5 × 10                       Staphylococ-                                                                          Potassium sorbate                                                                          Methyl 1-(butylcarba-                                                                       95/5  500   32 × 10                      cus aureus         moyl)-2-benzimidazole-                                                                      95/5  1000  10 × 10                                         carbamate    90/10 500   19 × 10                                                      90/10 1000  0                                                                  80/20 500   28 × 10                                                      80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   25 × 10.sup.7                                                100/0 1000  9 × 10.sup.5                 Staphylococ-                                                                          Potassium sorbate                                                                          Methyl 1-(butylcarba-                                                                       0/100 25    7 × 10.sup.6                 cus aureus         moyl)-2-benzimidazole-                                                                      0/100 50    9 × 10.sup.4                                    carbamate    0/100 100   12 × 10.sup.2                                                0/100 200   5 × 10                       Staphylococ-                                                                          Dehydroacetate                                                                             Methyl 1-(butylcarba-                                                                       95/5  500   30 × 10                      cus aureus         moyl)-2-benzimidazole-                                                                      95/5  1000  9 × 10                                          carbamate    90/10 500   15 × 10                                                      90/10 1000  0                                                                  80/20 500   15 × 10                                                      80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   22 × 10.sup.5                                                100/0 1000  6 × 10.sup.3                                                 0/100 25    7 × 10.sup.6                                                 0/100 50    9 × 10.sup.4                                                 0/100 100   12 × 10.sup.2                                                0/100 200   5 × 10                       Escherichia                                                                           Sodium dehydroacetate                                                                      Tetrachloroisophthalo-                                                                      95/5  500   9                                  coli               nitrile      95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   7 × 10.sup.8                                                 100/0 1000  9 × 10.sup.7                                                 0/100 25    2 × 10.sup.5                                                 0/100 50    9 × 10.sup.4                                                 0/100 100   7 × 10.sup.2                                                 0/100 200   3 × 10                       Escherichia                                                                           Potassium sorbate                                                                          Tetrachloroisophthalo-                                                                      95/5  500   25                                 coli               nitrile      95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   6 × 10.sup. 9                                                100/0 1000  12 × 10.sup.7                Escherichia                                                                           Potassium sorbate                                                                          Tetrachloroisophthalo-                                                                      0/100 25    2 × 10.sup. 5                coli               nitrile      0/100 50    9 × 10.sup.4                                                 0/100 100   7 × 10.sup.2                                                 0/100 200   3 × 10                       Escherichi                                                                            Dehydroactic acid                                                                          Tetrachloroisophthalo-                                                                      95/5  500   15                                 coli               nitrile      95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   13 × 10.sup.8                                                100/0 1000  31 × 10.sup.6                                                0/100 25    2 × 10.sup.5                                                 0/100 50    9 × 10.sup.4                                                 0/100 100   7 × 10.sup.2                                                 0/100 200   3 × 10                       Pseudomonas                                                                           Sodium dehydroactate                                                                       8-Hydroxyquinoline                                                                          95/5  500   9 × 10                       aeruginosa         sulfate      95/5  1000  0                                                                  90/10 500   5 × 10                                                       90/10 1000  0                                                                  80/20 500   8 × 10                                                       80/20 1000  0                                                                  60/40 500   4 × 10                                                       60/40 1000  0                                                                  100/0 500   15 × 10.sup.8                                                100/0 1000  2 × 10.sup.7                                                 0/100 25    22 × 10.sup.6                                                0/100 50    21 × 10.sup.4                                                0/100 100   15 × 10.sup.2                                                0/100 200   4 × 10                       Pseudomonas                                                                           Potassium sorbate                                                                          8-Hydroxyquinoline                                                                          95/5  500   18 × 10                      aeruginosa         sulfate      95/5  1000  4                                                                  90/10 500   16 × 10                                                      90/10 1000  0                                  Pseudomonas                                                                           Potassium sorbate                                                                          8-Hydroxyquinoline                                                                          80/20 500   17 × 10                      auruginosa         sulfate      80/20 1000  0                                                                  60/40 500   16 × 10                                                      60/40 1000  0                                                                  100/0 500   15 × 10.sup.10                                               100/0 1000  7 × 10.sup.8                                                 0/100 25    22 × 10.sup.6                                                0/100 50    21 × 10.sup.4                                                0/100 100   15 × 10.sup.2                                                0/100 200   4 × 10                       Pseudomonas                                                                           Sorbic acid 8-Hydroxyquinoline                                                                          95/5  500   95 × 10                      aeruginosa         sulfate      95/5  1000  10                                                                 90/10 500   21 × 10                                                      90/10 1000  8                                                                  80/20 500   17 × 10                                                      80/20 1000  0                                                                  60/40 500   14 × 10                                                      60/40 1000  0                                  Pseudomonas                                                                           Sorbic acid 8-Hydroxyquinoline                                                                          100/0 500   9 × 10.sup.9                 aeruginosa         sulfate      100/0 1000  8 × 10.sup.7                                                 0/100 25    22 × 10.sup.6                                                0/100 50    21 × 10.sup.4                                                0/100 100   15 × 10.sup.2                                                0/100 200   4 × 10                       Pseudomonas                                                                           Sodium dehydroacetate                                                                      p-Chloro-m-xylenol                                                                          95/5  500   15 × 10                      aeruginosa                      95/5  1000  0                                                                  90/10 500   13 × 10                                                      90/10 1000  0                                                                  80/20 500   12 × 10                                                      80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   15 × 10.sup.8                                                100/0 1000  2 × 10.sup.7                                                 0/100 25    8 × 10.sup.9                                                 0/100 50    15 × 10.sup.6                                                0/100 100   18 × 10.sup.4                                                0/100 200   13 × 10.sup.2                Pseudomonas                                                                           Potassium sorbate                                                                          p-Chloro-m-xylenol                                                                          95/5  500   20 × 10                      aeruginosa                      95/5  1000  7                                                                  90/10 500   17 × 10                                                      90/10 1000  5                                                                  80/20 500   15 × 10                                                      80/20 1000  5                                                                  60/40 500   3 × 10                                                       60/40 1000  0                                                                  100/0 500   15 × 10.sup.10                                               100/0 1000  7 × 10.sup.8                                                 0/100 25    8 × 10.sup.9                                                 0/100 50    15 × 10.sup.6                                                0/100 100   18 × 10.sup.4                                                0/100 200   13 × 10.sup.2                Pseudomonas                                                                           Sorbic acid p-Chloro-m-xylenol                                                                          95/5  500   18 × 10                      aeruginosa                      95/5  1000  5                                                                  90/10 500   10 × 10                                                      90/10 1000  0                                                                  80/20 500   9 × 10                                                       80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   9 × 10.sup.9                                                 100/0 1000  8 × 10.sup.7                                                 0/100 25    8 × 10.sup.9                                                 0/100 50    15 × 10.sup.6                                                0/100 100   18 × 10.sup.4                                                0/100 200   13 × 10.sup.2                __________________________________________________________________________

EXAMPLE 2

A 5% aqueous solution of starch was prepared and sterilized, and 100 ml. portions thereof were poured into 200 ml. bottles. After adding a prescribed amount of an antibacterial, antifungal composition consisting of the components (A) and (B) as shown in Table 2 to each bottle and thoroughly agitating, 1 ml. (number of fungi: 5×10⁶ fungi/ml.) of an aqueous suspension of fungi as shown in Table 2 was added to each bottle and was agitated again. The thus prepared aqueous solution contained 5×10⁴ fungi per gram. The bottles were then sealed and allowed to stand at 30° C. for a week. The state of the growth of fungi was observed by measuring the number of fungi in 1 g. of the aqueous solution.

The results are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                                           Amount of                                       Antibacterial, antifungal composition                                                                         composition                                                                          Number of                                                          (A)/(B)                                                                              added fungi                              Fungi  Component (A)                                                                              Component (B)                                                                               by weight                                                                            (p.p.m.)                                                                             (fungi/g.)                         __________________________________________________________________________     Trichoderma                                                                           Sodium dehydroacetate                                                                      N-(fluorodichloro-                                                                          95/5  100   4 × 10                       viride             methylthio)phthalimide                                                                      95/5  500   0                                                                  90/10 100   2 × 10                                                       90/10 500   0                                                                  80/20 100   8                                                                  80/20 500   0                                                                  60/40 100   0                                                                  100/0 100   29 × 10.sup.8                                                100/0 500   34 × 10.sup.5                                                0/100 5     7 × 10.sup.7                                                 0/100 25    16 × 10.sup.6                                                0/100 50    33 × 10.sup.4                                                0/100 100   5 × 10.sup.2                 Trichoderma                                                                           Potassium sorbate                                                                          N-(fluorodichloro-                                                                          95/5  100   8 × 10                       viride             methylthio)phthalimide                                                                      95/5  500   0                                                                  90/10 100   5 × 10                                                       90/10 500   0                                                                  80/20 100   7                                  Trichoderma                                                                           Potassium sorbate                                                                          N-(fluorodichloro-                                                                          80/20 500   0                                  viride             methylthio)phthalimide                                                                      60/40 100   0                                                                  100/0 100   27 × 10.sup.10                                               100/0 500   9 × 10.sup.8                                                 0/100 5     7 × 10.sup.7                                                 0/100 25    16 × 10.sup.6                                                0/100 50    33 × 10.sup.4                                                0/100 100   5 × 10.sup.2                 Trichoderma                                                                           Dehydroacetic acid                                                                         N-(fluorodichloro-                                                                          95/5  100   3 × 10                       viride             methylthio)phthalimide                                                                      95/5  500   0                                                                  90/10 100   0                                                                  80/20 100   0                                                                  60/40 100   0                                                                  100/0 100   25 × 10.sup.8                                                100/0 500   30 × 10.sup.5                                                0/100 5     7 × 10.sup.7                                                 0/100 25    16 × 10.sup.6                                                0/100 50    33 × 10.sup.4                Trichoderma                                                                           Dehydroacetic acid                                                                         N-(fluorodichloro-                                                                          0/100 100   5 × 10.sup.2                 viride             methylthio)phthalimide                                      Cladosporium                                                                          Sodium dehydroacetate                                                                      Sodium o-phenylphenolate                                                                    95/5  500   8 × 10                       resinae                         95/5  1000  5                                                                  90/10 500   5                                                                  90/10 1000  0                                                                  80/20 500   5                                                                  80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   31 × 10.sup.6                                                100/0 1000  28 × 10.sup.3                                                0/100 25    8 × 10.sup.10                                                0/100 50    18 × 10.sup.8                                                0/100 100   34 × 10.sup.6                                                0/100 200   5 × 10                       Cladosporium                                                                          Potassium sorbate                                                                          Sodium o-phenylphenolate                                                                    95/5  500   15 × 10                      resinae                         95/5  1000  3                                                                  90/10 500   10× 10                       Cladosporium                                                                          Potassium sorbate                                                                          Sodium o-phenylphenolate                                                                    90/10 1000  0                                  resinae                         80/20 500   9                                                                  80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   13 × 10.sup.6                                                100/0 1000  25 × 10.sup.3                                                0/100 25    8 × 10.sup.10                                                0/100 50    18 × 10.sup.8                                                0/100 100   34 × 10.sup.6                                                0/100 200   5 × 10                       Cladosporium                                                                          Dehydroacetic acid                                                                         Sodium o-phenylphenolate                                                                    95/5  500   7 × 10                       resinae                         95/5  1000  0                                                                  90/10 500   4                                                                  90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   10 × 10.sup.5                                                100/0 1000  9 × 10.sup.3                 Cladosporium                                                                          Dehydroacetic acid                                                                         Sodium o-phenylphenolate                                                                    0/100 25    8 × 10.sup.10                resinae                         0/100 50    18 × 10.sup.8                                                0/100 100   34 × 10.sup.6                                                0/100 200   5 × 10                       Aspergillus                                                                           Sodium dehydroacetate                                                                      2-(4-Thiazolyl)-1H-                                                                         95/5  500   7 × 10                       niger              benzimidazole                                                                               95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   18 × 10.sup.10                                               100/0 1000  30 × 10.sup.4                                                0/100 25    37 × 10.sup.8                                                0/100 50    18 × 10.sup.5                                                0/100 100   11 × 10.sup.3                                                0/100 200   4 × 10                       Aspergillus                                                                           Potassium sorbate                                                                          2-(4-Thiazolyl)-1H-                                                                         95/5  500   21 × 10                      niger              benzimidazole                                                                               95/5  1000  3                                                                  90/10 500   3 × 10                                                       90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   7 × 10.sup.10                                                100/0 1000  37 × 10.sup.8                                                0/100 25    37 × 10.sup.8                                                0/100 50    18 × 10.sup.5                                                0/100 100   11 × 10.sup.3                                                0/100 200   4 × 10                       Aspergillus                                                                           Dehydroacetic acid                                                                         2-(4-Thiazolyl)-1H-                                                                         95/5  500   5 × 10                       niger              benzimidazole                                                                               95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   17 × 10.sup.10               Aspergillus                                                                           Dehydroactic acid                                                                          2-(4-Thiazolyl)-1H-                                                                         100/0 1000  25 × 10.sup.4                niger              benzimidazole                                                                               0/100 25    37 × 10.sup.8                                                0/100 50    18 × 10.sup.5                                                0/100 100   11 × 10.sup.3                                                0/100 200   4 × 10                       Penicillium                                                                           Sodium dehydroacetate                                                                      Methyl-1-(butylcarba-                                                                       95/5  500   23 × 10                      citrinum           moyl)-2-benzimidazole-                                                                      95/5  1000  8                                                     carbamate    95/5  1000  8                                                                  90/10 500   2 × 10                                                       90/10 1000  0                                                                  80/20 5000  5                                                                  80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   17 × 10.sup.5                                                100/0 1000  35 × 10.sup.4                                                0/100 25    13 × 10.sup.8                                                0/100 50    19 × 10.sup.6                                                0/100 100   9 × 10.sup.3                                                 0/100 200   3 × 10                       Pencillium                                                                            Potassium sorbate                                                                          Methyl 1-(butylcarba-                                                                       95/5  500   19 × 10                      citrinum           moyl)-2-benzimidazole-                                                                      95/5  1000  9                                                     carbamate    90/10 500   10 × 10                                                      90/10 1000  1                                                                  80/20 500   7                                                                  80/20 1000  0                                                                  60/40 500   0                                                                  100/0 500   4 × 10.sup.9                                                 100/0 1000  12 × 10.sup.7                                                0/100 25    13 × 10.sup.8                                                0/100 50    19 × 10.sup. 6                                               0/100 100   9 × 10.sup.3                                                 0/100 200   3 × 10                       Penicillium                                                                           Sorbic acid Methyl 1-(butylcarba-                                                                       95/5  500   8 × 10                       citrinum           moyl)-2-benzimidazole-                                                                      95/5  1000  5                                                     carbamate    90/10 500   5 × 10                                                       90/10 1000  2                                  Penicillium                                                                           Sorbic acid Methyl 1-(butylcarba-                                                                       80/20 500   0                                  citrinum           moyl)-2-benzimidazole                                                                       60/40 500   0                                                     carbamate    100/0 500   7 × 10.sup.7                                                 100/0 1000  40 × 10.sup.5                                                0/100 25    13 × 10.sup.8                                                0/100 50    19 × 10.sup.6                                                0/100 100   9 × 10.sup.3                                                 0/100 200   3 × 10                       Aspergillus                                                                           Sodium dehydroacetate                                                                      Tetrachloroisophthalo-                                                                      95/5  100   2                                  niger              nitrile      95/5  500   0                                                                  90/10 100   0                                                                  80/20 100   0                                                                  60/40 100   0                                                                  100/0 100   25 × 10.sup.10                                               100/0 500   18 × 10.sup.7                                                0/100 5     7 × 10.sup.4                                                 0/100 25    8 × 10.sup. 3                                                0/100 50    3 × 10                       Aspergillus                                                                           Potassium sorbate                                                                          Tetrachloroisophthalo-                                                                      95/5  100   13 × 10                      niger              nitrile      95/5  500   0                                                                  90/10 100   0                                                                  80/20 100   0                                                                  60/40 100   0                                                                  100/0 100   33 × 10.sup.11                                               100/0 500   7 × 10.sup.10                                                0/100 5     7 × 10.sup.4                                                 0/100 25    8 × 10.sup.3                                                 0/100 50    3 × 10                       Aspergillus                                                                           Sorbic acid Tetrachloroisophthalo-                                                                      95/5  100   10 × 10                      niger              nitrile      95/5  500   0                                                                  90/10 100   0                                                                  80/20 100   0                                                                  60/40 100   0                                                                  100/0 100   32 × 10.sup.10               Aspergillus                                                                           Sorbic acid Tetrachloroisophthalo-                                                                      0/100 5     7 × 10.sup.4                 niger              nitrile      0/100 25    3 × 10.sup.3                                                 0/100 50    3 × 10                                                                   - Aspergillus Sodium                                                           dehydroacetate 8-Hydroxyquinol                                                 ine 95/5 500 3                     niger              sulfate      95/5  1000  0                                                                  90/10 500   2                                                                  90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   18 × 10.sup.7                                                100/0 1000  30 × 10.sup.4                                                0/100 25    10 × 10.sup.6                                                0/100 50    7 × 10.sup.3                                                 0/100 100   6 × 10.sup.2                                                 0/100 200   6 × 10                       Aspergillus                                                                           Potassium sorbate                                                                          8-Hydroxyquinoline                                                                          95/5  500   13 × 10                      niger              sulfate      95/5  1000  0                                                                  90/10 500   8                                                                  90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   7 × 10.sup.10                                                100/0 1000  37 × 10.sup.8                                                0/100 25    10 × 10.sup.6                                                0/100 50    7 × 10.sup.3                                                 0/100 100   6 × 10.sup.2                                                 0/100 200   6 × 10                       Aspergillus                                                                           Dehydroacetic acid                                                                         8-Hydroxyquinoline                                                                          95/5  500   2                                  niger              sulfate      95/5  1000  0                                                                  90/10 500   2                                                                  90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                  Aspergillus                                                                           Dehydroacetic acid                                                                         8-Hydroxyquinoline                                                                          100/0 500   10 × 10.sup.7                niger              sulfate      100/0 1000  25 × 10.sup.4                                                0/100 25    10 × 10.sup.6                                                0/100 50    7 × 10.sup.3                                                 0/100 100   6 × 10.sup.2                                                 0/100 200   6 × 10                       Aspergillus                                                                           Sodium dehydroacetate                                                                      p-Chloro-m-xylenol                                                                          95/5  500   10 × 10                      niger                           95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   18 × 10.sup.7                                                100/0 1000  30 × 10.sup.4                                                0/100 25    14 × 10.sup.9                                                0/100 50    16 × 10.sup.4                                                0/100 200   5 × 10                       Aspergillus                                                                           Potassium sorbate                                                                          p-Chloro-m-xylenol                                                                          95/5  500   15 × 10                      niger                           95/5  1000  0                                                                  90/10 500   5 × 10                                                       90/10 1000  0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   7 × 10.sup.10                                                100/0 1000  37 × 10.sup.8                                                0/100 25    14 × 10.sup.9                                                0/100 50    16 × 10.sup.6                                                0/100 100   12 × 10.sup.4                                                0/100 200   5 × 10                       Aspergillus                                                                           Dehydroacetic acid                                                                         p-Chloro-m-xylenol                                                                          95/5  500   6 × 10                       niger                           95/5  1000  0                                                                  90/10 500   0                                                                  80/20 500   0                                                                  60/40 500   0                                                                  100/0 500   10 × 10.sup.7                Aspergillus                                                                           Dehydroacetic acid                                                                         p-Chloro-m-xylenol                                                                          100/0 1000  25 × 10.sup.4                niger                           0/100 25    14 × 10.sup.9                                                0/100 50    16 × 10.sup.6                                                0/100 100   12 × 10.sup.4                                                0/100 200   5 × 10                       __________________________________________________________________________

EXAMPLE 3

A 2% of aqueous solution of carboxymethyl cellulose was prepared and adjusted to pH 7. After adding an antibacterial, antifungal composition consisting of the components (A) and (B) to the solution in a concentration as shown in Table 3, a slight amount of a putrid carboxymethyl cellulose was added to the solution. The solution was stored in an air-conditioned room at 37° C. and the putrefaction of the solution was obserbed with the lapse of time.

The results are shown in Table 3, in which symbols are as follows:

-: No putrefaction

+: Putrefaction

                                      TABLE 3                                      __________________________________________________________________________     Antibacterial, antifungal composition                                                                        Time elapsed                                                 Concent-          Concent-                                                     ration            ration                                                                              After                                                                              After                                                                               After                              Component (A)                                                                              (p.p.m.)                                                                            Component (B)                                                                               (p.p.m.)                                                                            1 week                                                                             2 weeks                                                                             3 weeks                            __________________________________________________________________________     Sodium dehydroacetate                                                                      500  Sodium o-phenylphenolate                                                                    10   --  --   --                                 Potassium sorbate                                                                          500  Sodium o-phenylphenolate                                                                    50   --  --   --                                 --          0    Sodium o-phenylphenolate                                                                    100  --  +    +                                  Sodium dehydroacetate                                                                      2000 --           0    --  --   +                                  Potasssium sorbate                                                                         2000 --           0    --  +    +                                  --          0    --           0    +   +    +                                  __________________________________________________________________________

EXAMPLE 4

An antibacterial, antifungal composition was added to a 6% aqueous solution of glue in a concentration as shown in Table 4. The solution was stored in an air-conditioned room at 50° C. and the decrease of the viscosity due to putrefaction was observed with the lapse of time.

The results are shown in Table 4, in which symbols are as follows:

-: No decrease of viscosity

+: Decrease of viscosity

                                      TABLE 4                                      __________________________________________________________________________     Antibacterial, antifungal composition                                                                        Time elapsed                                                 Concent-          Concent-                                                     ration            ration                                                                              After                                                                              After                                                                               After                              Component (A)                                                                              (p.p.m.)                                                                            Component (B)                                                                               (p.p.m.)                                                                            1 week                                                                             2 weeks                                                                             3 weeks                            __________________________________________________________________________     Sodium dehydroacetate                                                                      1000 Sodium o-phenylphenolate                                                                    50   --  --   --                                 Potassium sorbate                                                                          2000 Sodium o-phenylphenolate                                                                    50   --  --   --                                 --          0    Sodium o-pehnylphenolate                                                                    200  +   +    +                                  Sodium dehydroacetate                                                                      5000 --           0    --  --   +                                  Potassium sorbate                                                                          5000 --           0    --  --   +                                  --          0    --           0    +   +    +                                  __________________________________________________________________________

EXAMPLE 5

An antibacterial, antifungal composition was added to an ethylene-vinyl acetate copolymer emulsion containing polyvinyl alcohol as an emulsifier in a concentration as shown in Table 5. A slight amount of a putrid emulsion was added to the emulsion and the number of cells was immediately measured. The emulsion was then stored in an air-conditioned room at 30° C., and after 3 weeks, the number of cells in the emulsion was measured again to determine the preservative and fungicidal effects.

The results are shown in Table 5.

                                      TABLE 5                                      __________________________________________________________________________     Antibacterial, antifungal composition                                                 Concent-     Concent-                                                                            Number of cells (cell/g.)                                    ration       ration                                                                              Before storage After 3 weeks                          Component (A)                                                                         (p.p.m.)                                                                            Component (B)                                                                          (p.p.m.)                                                                            Fungi                                                                               Yeast                                                                               Bacteria                                                                            Fungi                                                                               Yeast                                                                               Bacteria                     __________________________________________________________________________     Potassium de-                                                                         3000 Sodium o-phe-                                                                          100  51 × 10.sup.6                                                                 15 × 10.sup.6                                                                 7 × 10.sup.3                                                                  <10.sup.2                                                                           <10.sup.2                                                                           2 × 10.sup.2           hydroacetate                                                                               nylphenolate                                                       Potassium                                                                             4000 Sodium o-phe-                                                                          200  35 × 10.sup.6                                                                 19 × 10.sup.6                                                                 5 × 10.sup.3                                                                  <10.sup.2                                                                           <10.sup.2                                                                           4 × 10.sup.2           sorbate     nylphenolate                                                        --    0    Sodium o-phe-                                                                          1000 25 × 10.sup.6                                                                 19 × 10.sup.6                                                                 9 × 10.sup.3                                                                  31 × 10.sup.5                                                                 22 × 10.sup.5                                                                 9 × 10.sup.3                       nylphenolate                                                       Sodium de-                                                                            5000 --      0    30 × 10.sup.6                                                                 26 × 10.sup.6                                                                 6 × 10.sup.3                                                                  72 × 10.sup.4                                                                 18 × 10.sup.4                                                                 6 × 10.sup.3           hydroacetate                                                                   Potassium                                                                             5000 --      0    17 × 10.sup.6                                                                 24 × 10.sup.6                                                                 6 × 10.sup.3                                                                  10 × 10.sup.6                                                                 29 × 10.sup.5                                                                 5 × 10.sup.3           sorbate                                                                         --    0    --      0    51 × 10.sup.6                                                                 18 × 10.sup.6                                                                 8 × 10.sup.3                                                                  23 × 10.sup.7                                                                 25 × 10.sup.6                                                                 8 × 10.sup.3           __________________________________________________________________________

EXAMPLE 6

A 10% aqueous solution of a polyvinyl alcohol sizing agent was prepared and divided into three portions. To the first portion was added no medicine, to the second portion was added 2,000 p.p.m. of sodium dehydroacetate, and to the third portion were added 1,000 p.p.m. of sodium dehydroacetate and 100 p.p.m. of p-chloro-m-xylenol. Epicoccum sp. was inoculated to each of the three portions, and they were placed in an incubator at 30° C. and allowed to stand for 14 days.

In the first and second portions, development of fungi was observed after 3 and 5 days, respectively, but in the third portion no development of fungi was observed.

The above procedure was repeated except that, as the component (B), 2-(4-thiazolyl)-1H-benzimidazole, 8-hydroxyquinoline sulfate, methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate, tetrachloroisophthalonitrile or N-(fluorodichloromethylthio)phthalimide was employed instead of p-chloro-m-xylenol. The same results as above were obtained with respect to all the above compounds.

EXAMPLE 7

The procedures of Example 6 were repeated except that potassium sorbate was employed instead of sodium dehydroacetate.

With respect to all tests using six components (B) in Example 6, in the first and second portions development of fungi was observed after 4 and 6 days respectively, but in the third portion no development of fungi was observed.

EXAMPLE 8

An antibacterial, antifungal composition was prepared by admixing 95 g. of sodium dehydroacetate as the component (A) and 5 g. of the component (B) shown in Table 6. The composition was added to a 18% solution of a crotonic acid-vinyl acetate copolymer in a concentration of 2,500 p.p.m., 5,000 p.p.m. or 7,500 p.p.m. to give three kinds of the coating solutions.

Each solution was sprayed onto two sides of a fancy mat (10×10 cm.) in an amount of 2 g. on each side, and was then dried at 140° C. for 2 minutes.

The coated fancy mats were allowed to stand under a saturated humidity at 25° C., and the state of the growth of fungi was observed with the lapse of time.

The results are shown in Table 6, in which symbols are as follows:

-: No growth

±: A little growth

+: Growth (The more the number of the symbol +, the larger the growth.)

                                      TABLE 6                                      __________________________________________________________________________                      Concentration                                                                  of composition                                                                         Days elapsed                                          Component (B)    (p.p.m.)                                                                               5 6 7  8   10   12    14                              __________________________________________________________________________     p-Chloro-m-xylenol                                                                              0       - - +   ++ +++  +++++ +++++                                            2500    - - ±                                                                              +   +++  +++   ++++                                             5000    - - -  ±                                                                               +    ++    +++                                              7500    - - -  -   -    -     -                               2-(4-Thiazolyl)-1H-benzimidazole                                                                0       - + ++ +++ ++++ +++++ +++++                                            2500    - - +  +   +++  +++   ++++                                             5000    - - -  ±                                                                               +    ++    +++                                              7500    - - -  -   -    -     -                               8-Hydroxyquinoline sulfate                                                                      0       - + ++ +++ ++++ +++++ +++++                                            2500    - - +  +   +++  +++   ++++                                             5000    - - -  ±                                                                               +    ++    +++                                              7500    - - -  -   -    -     -                               Methyl 1-(butylcarbamoyl)-2-benz-                                                               0       - + ++ +++ ++++ +++++ +++++                           imidazolecarbamate                                                                              2500    - - +  +   +++  +++   ++++                                             5000    - - -  ±                                                                               +    ++    +++                                              7500    - - -  -   -    -     -                               Tetrachloroisophthalonitrile                                                                    0       - + + +                                                                               +++ ++++ +++++ +++++                                            2500    - - ±                                                                              +   +++  +++   ++++                                             5000    - - -  -   ± +     ++                                               7500    - - -  -   -    -     -                               N-(fluorodichloromethylthio)-                                                                   0       - + ++ +++ ++++ +++++ +++++                           phthalimide                                                                                     2500    - ±                                                                             +  +   +++  +++   ++++                                             5000    - - -  ±                                                                               +    ++    +++                                              7500    - - -  -   -    -     -                               __________________________________________________________________________

EXAMPLE 9

A sizing solution containing 5% of wheat starch and a sizing solution containing 5% of casein were prepared, and thereto was added an antibacterial or antifungal agent as shown in Table 7. After adding a suspension of fungi consisting of Aspergillus niger, Penicillium citrinum, Cladosporium herbaum and Chaetomium globosum to each of the sizing solutions, the sizing solutions were placed in an incubator at 28° C. and the state of the growth of fungi was observed with the lapse of time.

The results are shown in Table 7, in which symbols are as follows:

-: No growth

±: A little growth

+: Growth (The more the number of the symbol +, the larger the growth.)

                                      TABLE 7                                      __________________________________________________________________________     Sizing                       Incubation days                                   solution                                                                              Antibacterial, antifungal agent                                                                      0 4 7   14   21   28                              __________________________________________________________________________     Wheat starch                                                                          None                  - + +++ ++++ ++++ ++++                            Casein "                     - - ++  +++  ++++ ++++                            Wheat starch                                                                          Sodium dehydroacetate (500 p.p.m.)                                                                   - - ±                                                                               ++   +++  +++                             Casein "                     - - -   +    ++   +++                             Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         p-Chloro-m-xylenol (25 p.p.m.)                                                                       - - -   -    -    -                               Casein Sodium dehydroacetate (475 p.p.m.) and                                         p-Chloro-m-xylenol (25 p.p.m.)                                                                       - - -   -    -    -                               Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         2-(4-Thiazolyl)-1H-benzimidazole (25 p.p.m.)                                                         - - -   -    -    -                               Casein Sodium dehydroacetate (475 p.p.m.) and                                         2-(4-Thiazolyl)-1H-benzimidazole (25 p.p.m.)                                                         - - -   -    -    -                               Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         8-Hydroxyquinoline sulfate (25 p.p.m.)                                                               - - -   -    -    -                               Casein Sodium dehydroacetate (475 p.p.m.) and                                         8-Hydroxyquinoline sulfate (25 p.p.m.)                                                               - - -   -    -    -                               Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         Methyl 1-(butylcarbamoyl)-2-benzimidazole                                                            - - -   -    -    -                                      carbamate (25 p.p.m.)                                                   Casein Sodium dehydroacetate (475 p.p.m.) and                                         Methyl 1-(butylcarbamoyl)-2-benzimidazole                                                            - - -   -    -    -                                      carbamate (25 p.p.m.)                                                   Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         Tetrachloroisophthalonitrile (25 p.p.m.)                                                             - - -   -    -    -                               Casein Sodium dehydroacetate (475 p.p.m.) and                                         Tetrachloroisophthalonitrile (25 p.p.m.)                                                             - - -   -    -    -                               Wheat starch                                                                          Sodium dehydroacetate (475 p.p.m.) and                                         N-(fluorodichloromethylthio)phthalimide                                                              - - -   -    -    -                                      (25 p.p.m.)                                                             Casein Sodium dehydroacetate (475 p.p.m.) and                                         N-(fluorodichloromethylthio)phthalimide                                                              - - -   -    -    -                                      (25 p.p.m.)                                                             __________________________________________________________________________ 

What we claim is:
 1. An antibacterial and antifungal composition comprising a mixture of:(A) at least one member selected from the group consisting of dehydroacetic acid, and its alkali metal salts; and (B) tetrachloroisophthalonitrile, wherein the weight ratio of component (A) to component (B) is in the range of 95/5 to 60/40. 